Process for manufacturing textile agents



Patented Sept, 39, 1939 i raccass non mmrrncrnnnee r aenn'r MeindertDanica Rozenbroeh, Delden, T wenthe, Over-Heel, Netherlands No Drawing.Application April 12, 1937, Seriai No. 136,513. In the NetherlandsFebruary 2'3,

7 @iaims.

It has been proposed in British specification No. 409,598 and Dutchspecification No. 36,289 to convert higher alcohols into thecorresponding esters of acids derived from phosphorus and to sulphonatethe said esters whereby products are obtained which contain sulphur aswell as phosphorus in organically bound form.

The invention has for its object a process for manufacturing textileagents, such as cleansing,

10 wetting out,.foaming, dispersing, equalizing and bleaching agentswhich comprises sulphonating' a compound derived from a polyhydricalcohol by esterifying at least one hydroxy group of the Same with anacid derived from phosphorus so as to produce a primary ester of thesaid acid,

and esteriiying or etherifying at least one remaining hydroxy group ofthe alcohol with a fatty acid or a mcnohydric alcohol having at least 6carbon atoms.

The invention also relates to textile agents con sisting of orcontaining the compounds specified above.

The ethers or esters sulfonated according to the invention arerepresented by the following for- 26 mulae (1:) R000 omen, o P on (b) Ro omen, o P (on),

e a coo cnlonon on, o r (on):

' (d) a 0 on; error: on, o I" on It being the alkyl group with at least6 carbon atoms present in the fatty acid or the monohydric alcohol fromwhich the esters or etherswith the polyhydric alcohol are derived.

In the formulae given above the-acid used is phosphorous acid; however,similar compounds can be derived from other acids containing phosphorus,especially phosphoric acid.

The monohydric alcohol used may be saturated or unsaturated, elaidinisedor not, and primary,

secondary or tertiary. If desired the alcohol may contain othersubstituents, e. g. halogen atoms, acyl or other groups. They may bemanufactured 5o artificially or they may be obtained from naturalproducts, e. g. waxes. Cholesterol, isocholesterol and similar alcoholsof a more complicated nature which can be obtained from waxes are alsosuitable for the purpose.

55 The higher fatty acids may also be saturated (or. ace-rec)orunsaturated and elaidinised or not. They may cgntain one or morehydroxy groups or other substituents, e. g. halogen atoms, acyl or othergroups. 4

As polyhydric alcohols besides the glycol and 5 lycerol mentioned in theabove formulae, erythritol,.propene diol, 2.3 butanediol, the alcoholsobtained by reduction of sugars etc., may be used.' Instead of thepolyhydric alcohols one can also use partial ethers of the polyhydricalcohols 10 which contain at least two free hydroxy groups, e. g. thepolyglycol or polyglycerol ether, Aminoethers with at least two freehydroxy groups, e. g. triethanol amine, are also suitable.

The above described phosphorus containing it! ethers or esters are thensulphonated according to methods known per se. The sulphonation can becarried out with sulphuric acid or other sulphonating agents, e. g.oleum, sulphuric acid anhydride or chlorsulphonic acid, alone ortogether with water binding agents, e. g. phosphorus pentoxide. Thesulphonating agent can be added to the material to be sulphonated orvice versa.

The compounds obtained according to the in- Vention are distinguishedfrom the substances obtained according to prior processes by thepresence of a monoesterified phosphoric acid or phosphorous acid group,i. e. a group resulting if a polybasic acid of this character isesterified with one hydroxy group of an alcohol. The presence of thismonoesterified acid group has a favourable infiuence on the propertiesof the com-' pounds obtained. Sc e. g. the clearness of a dilutesolution in hard water after standing is better. The solutions in softwater are even absolutely 85 clear.

Not only the solubility but also the resistance against moderatelyconcentrated alkaline solutions, e. g. a sodium hydroxide solution of15%, even at the boiling point,.is improved.

' Suitable starting materials are mixtures of fatty acids and fatalcohols as e. g. obtained by the saponification oi waxes and by theincomplete reduction of fatty acids to alcohols. The

fatty acid may e. g. be esterified and the alcohol etherified both withglycol, and in the mixture obtained the ester and the ether may beconverted into the corresponding monoesterifled phosphorus compounds andfinally the mixture may be sulphonated.

The sulphonated compounds obtained according to the invention can beconverted into substances containing active oxygen by treating thenon-neutralised sulphonation product with a peroxide and neutralisingthe reaction product, or

by reacting the neutrallsed product with a peroxide. The product therebyacquires bleaching properties.

. 'The invention will. be illustrated by the following examples:

Example I 20 parts by weight of the monostearyl ether of glycol inmolten condition are poured into 11 parts by weight of PC13 and slowlyheated for some time until the development of gas is substantiallyfinished. After-cooling, 20 parts by weight of sulphuric acid are slowlyadded to the reaction mixture, the mass being well stirred andtemperature.

good wetting out agent.

care being taken that the temperature generally does not exceed 35 C.The sulphonate is then freed from the excess of acid by washing with amixture of water and Glaubers salt and neutralised.

Example II 225 parts by weight of the monolaurylether of glycol areesterified with 150.parts by weight of P205 and then sulphonated with$250 parts by weight of sulphuric acid at a moderately elevated Theneutralised product is a very aivaeas organic acid derived fromphosphorus and sulfonating the resultant inorganic acid ester.

3. The process which comprises reacting an ester made from a polyhyd'ricalcohol and a high molecular weight fatty acid, with an inorganic acidderived from phosphorus, and suii'onating the resultant inorganic acidester.

4. The process which comprises reacting a mixture of (a) an ether madefrom a polyhydric alcohol and a high molecular weight aliphatic alcoholand (b) an ester made from a polyhydric alcohol and a high molecularweight fatty acid with an inorganic acid derived from phosphorus andsulfonating the resultant inorganic acid ester mixture, the-said mixtureof an ether made from a polyhydric alcohol and a high molecular weightaliphatic alcohol and an ester made from a polyhydric alcohol and a highmolecular weight fatty acid being obtained from a pre-existing mixtureof a high molecular weight aliphatic alcohol and a high molecular weightfatty acid by etherifying the said aliphatic alcohol and esterifying thesaid fatty acid in the mixture with a polyhydric alcohol.

5. Sulfonated esters made from a compound selected from the groupconsisting of (a) ethers made from a polyhydric alcohol and a highmolecular weight aliphatic alcohol and (b) esters made from a polyhydricalcohol and a high molecular weight fatty acid, and an inorganic acidderived from phosphorus.

6. Sulfonated esters made from an ether of a polyhydric alcohol and ahigh molecular weight aliphatic alcohol, and an inorganic acid derivedfrom phosphorus.

7. Sulfonated esters made from an ester of a 'polyhydric alcohol and ahigh molecular weight I CERTIFICATE QF-CORRECTION. Patentillo.2,175,658. September 19,1959.

'MEINDERT DANIUS ROZENBROEK.

It is hereby certified that the above numbered patent was erroneouslyissued to the inventor, said "Rozenbroek" as owner of the entireinterest therein, whereas said patent should have been issued toMeindert Danius Rozenbroek, of Delden, Twenthe, Overijsel, Netherlands,assignor, by direct and mesne assignments, .to himself and N. V.-Chemische Fabriekfie'rvo, a

Limited Liability Company, of Delden, Twente, Overijsel, Neth r I acorporation of the Netherlands, as shown by the record of assignments inthis office; and that the said Letters Patent shouldbe read with thiscorrectionv therein that the same may conform to the record of the casein the Patent Office v Signed and sealed this 2nd day of January, A. D.19to.

- Henry Van Arsdale,

Acting Commissioner of Patents.

